Enhanced electrochemical properties of nanocomposite polymer electrolyte based on copolymer with exfoliated clays

In this present work, a polymer electrolyte based on polymer/clay nanocomposite has been developed. Montmorillonite (MMT) clay was used as the filler. due to its special size in length and thickness, and its sandwich type structure. The obtained gel polymer electrolytes have high ionic conductivity up to 2.5 mS cm(-1) with high cationic transference number (about 0.64) at room temperature. The influences of the filler on the membrane morphology. the solvent uptake, the ionic conductivity, and the cation transport number were investigated, and thus the significant contribution from the exfoliated organophilic MMT was identified.

Poly(vinylidene fluoride-hexafluoropropylene)/organo-montmorillonite clays nanocomposite lithium polymer electrolytes

Polymer-clay nanocomposite (PCN) materials were prepared by intercalation of an alkyl-ammonium ion spacing/coupling agent and a polymer between the planar layers of a swellable-layered material, such as montmorillonite (MMT). The nanocomposite lithium polymer electrolytes comprising such PCN materials and/or a dielectric solution (propylene carbonate) were prepared and discussed. The chemical composition of the nanocomposite materials was determined with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, which revealed that the alkyl-ammonium ion successfully intercalated the layer of MMT clay, and thus copolymer poly(vinylidene fluoride-hexafluoropropylene) entered the galleries of montmorillonite clay. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of the lithium polymer electrolyte. Equivalent circuits were proposed to fit the EIS data successfully, and the significant contribution from MMT was thus identified. The resulting polymer electrolytes show high ionic conductivity up to 10(-3) S cm(-1) after felling with propylene carbonate.

Effects of surfactant loadings on the dispersion of clays in maleated polypropylene

A series of organically modified clays (OMCs) with a surfactant loading range from 0.625 to 2.5 times the cation exchange capacity (CEC) were melt-mixed with maleated polypropylene (PPMA). Wide-angle X-ray diffraction and transmission electron microscopy results of these narrocomposites show that dispersion of clays becomes unfavorable in the PPMA matrix during melt intercalation as the surfactant loading increases in the process of modifying clays, though larger interlayer distances are obtained in their corresponding OMCs. It is even important that clays uniformly disperse at the nanoscale level in the PPMA matrix when the surfactant loadings are below the CEC, which implies that incomplete exchange of inorganic cations in the process of modifying clay benefits the dispersion of clays in the PPMA matrix.

Flocculation and removal of the brown tide organism, Aureococcus anophagefferens (Chrysophyceae), using clays

Previous attempts to remove the brown tide organism, Aureococcus anophagefferens, through flocculation with clays have been unsuccessful, in spite of adopting concentrations and dispersal protocols that yielded excellent cell removal efficiency (RE>90%) with other species, so a study was planned to improve cell removal. Four modifications in clay preparation and dispersal were explored: 1) varying the salinity of the clay suspension; 2) mixing of the clay-cell suspension after clay addition; 3) varying of concentration of the initial clay stock; 4) pulsed loading of the clay slurry. The effect of salinity was dependent on the clay mineral type: phosphatic clay (IMC-P2) had a higher RE than kaolinite (H-DP) when seawater was used to disperse the clay, but H-DP removed cells more efficiently when suspended in distilled water prior to application. Mixing after dispersal approximately doubled RE for both clays compared to when the slurry was layered over the culture surface. Lowering the concentration of clay stock and pulsing the clay loading increased RE, regardless of mineral type. However, this increase was more apparent for clays dispersed in seawater than in distilled water. In general, application procedures that decrease the rate of self-aggregation among the clay particles and increase the collision frequency between clay particles and A. anophagefferens achieve higher cell removal efficiency. These empirical studies demonstrated that clays might be an important control option for the brown tide organism, given the proper attention to preparation, dispersal methods, environmental impacts, and the hydrodynamic properties of the system being treated. Implications for the treatment of brown tides in the field are discussed.

Comparison of salt titration and potentiometric titration methods for the determination of zero point of charge

the salt ritration metod was evaluated as a method to determine zpc in comparison with the potentiometric titration method for 26 soil with variable charge clays,i.e.,Oxisols and Ultisols from Thailand and Andisols from Japan. In addition to the determination of ST-pH0 as the zero point of charge, a calculation procedure was adopted here in order to acquire more information from the titration curve . fuithermore, for the purpose of cross-checking of zpc determined by the pt method, the st procedure was successively applied to the samples analyzed by the pt method.

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography-mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H-MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Bronsted acid sites on the H-MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT-rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced.

Specific determination of As(V) by an acid phosphatase-polyphenol oxidase biosensor

An original amperometric biosensor based on the simultaneous entrapment of acid phosphatase (AcP) and polyphenol oxidase (PPO) into anionic clays (layered double hydroxides) was developed for the specific detection of As(V). The functioning principle of the bienzyme electrode consisted of the successive hydrolysis of phenyl phosphate into phenol by AcP, followed by the oxidation of phenol into o-quinone by PPO. The phenyl phosphate concentration was, thus, monitored by potentiostating the biosensor at -0.2 V vs Ag/AgCl to detect amperometrically the generated quinone. The detection of As(V) was based on its inhibitory effect on AcP activity toward the hydrolysis of phenyl phosphate into phenol. The As(V) can be specifically determined in pH 6.0 acetate buffer without any interferences of As(III) or phosphate, the detection limit being 2 nM or 0.15 ppb after an incubation step for 20 min.

Yangtze- and Taiwan-derived sediments on the inner shelf of East China Sea

X-ray diffraction (XRD) mineralogical and grain-size analyses indicate that inner continental shelf sediments in the East China Sea (ECS) represent a unique mixing of clays derived from the Yangtze River and silts/sands from small western Taiwanese rivers. Taiwanese (e g., Choshui) clays (< 2 mu m) display no smectite but the best illite crystallinity and are only distributed along southeastern Taiwan Strait. Both Yangtze and Taiwanese river clays are illite-dominated, but the poor illite crystallinity and the presence of smectite and kaolinite indicate that Taiwan Strait clays are mainly Yangtze-dominated. In contrast, medium silts (20-35 mu m) and very fine sands (63-90 mu m) in the Taiwan Strait are characterized by low feldspar/quartz, low K-feldspar/plagioclase and high kaolinite/quartz, indicating their provenance from Taiwanese rivers. Taiwanese silts and sands are introduced primarily by the way of typhoon-derived floods and transported northward by the Taiwan Warm Current during summer-fall months. Yangtze clays, in contrast, are widely dispersed southward about 1000 km to the western Taiwan Strait, transported by the China Coastal Current during winter-spring months Since most Taiwan Strait samples were collected in May 2006, clay results in this paper might only represent the winter-spring pattern of the dispersal of Yangtze sediments. (C) 2009 Elsevier Ltd. All rights reserved.

Geochemical character and material source of sediments in the eastern Philippine Sea

Based upon analyses of grain-size, rare earth element (REE) compositions, elemental occurrence phases of REE, and U-series isotopic dating, the sediment characteristics and material sources of the study area were examined for the recently formed deep-sea clays in the eastern Philippine Sea. The analytical results are summarized as follows. (1) Low accumulation rate, poor sorting and roundness, and high contents of grains coarser than fine silt indicate relatively low sediment input, with localized material source without long distance transport. (2) The REE Contents are relatively high. Shale-normalized patterns of REE indicate weak enrichment in heavy REE (HREE), Ce-passive anomaly, and Eu-positive anomaly. (3) Elemental occurrence phases of REE between the sediments with and without crust are similar. REE mainly concentrate in residual phase and then in ferromanganese oxide phase. The light REE (LREE) enrichment, Ce-positive anomaly, and Eu-positive anomaly occur in residual phase. Ferromanganese oxide phase shows the characteristics of relatively high HREE content and Ce-passive anomaly. (4) There are differences in each above mentioned aspect between the sediments with and without ferromanganese crust. (5) Synthesizing the above characteristics and source discriminant analysis, the study sediments are deduced to mainly result from the alteration of local and nearby volcanic materials. Continental materials transported by wind and/or river (ocean) flows also have minor contributions.

A preliminary study on fingerprinting approach in marine sediment dynamics with the rare earth elements

Locating the quantitized natural sediment fingerprints is an important work for marine sediment dynamics study. The total of 146 sediment samples were collected from the Shelf of the East China Sea and five rivers, including Huanghe (Yellow), Changjiang (Yangtze), Qiantang, Ou and Min River. The sediment grain size and the contents of rare earth elements (REEs) were measured with laser particle size analyzer and ICP-MS technology. The results show that absolute REE content (Sigma REE) and the concentration ratio of light REEs to heavy REEs (L/HREE) are different in the sediments among those rivers. There are higher REE contents in being less than 2 m and 2-31 mu m fractions in the Changjiang Estuary surface sediments. The REE contents of bulk sediment are dominated by the corresponding values of those leading size-fractions. Sigma REE of sediment is higher close to the estuaries and declines seaward on the inner shelf of the East China Sea (ECS). The L/HREE ratio has a tendency of increase southward from 28 degrees N. Hydrodynamic conditions plays a predominate role on spacial distributions of the surficial sediment's REE parameters. In some situations, the currents tend to remove the coarser light grains from initial populations, as well as the deposit of the finer heavy mineral grains. In other situations, the currents will change the ratio of sediment constituents, such as ratio between silts and clays in the sediments. As a result, the various values of Sigma REE or L/HREE ratio in different bulk sediments are more affected by the change of size-fractions than source location. Under the long-term stable hydrodynamic environment, i.e., the East China Sea Shelf, new sediment transport model based on the size and density gradation concept may help to understand the spatial distribution patterns of REE parameters.

中国东部上第三系硬粘土的工程地质特性及边坡开挖工程环境效应研究

The engineering geological properties of Neogene hard clays and related engineering problems are frontiers in the fields of Engineering Geology, Soil Mechanics and Rock Mechanics. Recently, it has been recognized that Neogene hard clay is the intermediate type of material between the soil and the rock. Many aspects of them, such as sampling, testing, calculating and engineering process, are special, which could not be researched by means of theories and methods of traditional Soil Mechanics of Rock Mechanics. In order to get real knowledge and instruct the engineering practice, intersect studying of multiple disciplines, including Engineering Geology, Soil Mechanics and Rock Mechanics, etc., is necessary. Neogene hard clay is one of the important study objects of regional problem rocks & soils in our country, which extensively distributed in China, especially in Eastern China. Taking the related areas along the middle line of the Project of Transferring Water from the South to the North (e.g. Nanyang basin, Fangcheng-Baofeng area and Handan-Yongnian area), South-west of Shandong, Xu-Huai area and Beijing area, etc. as main study areas, the paper divided Neogene hard clays into reduction environment dominated origin and oxidation environment dominated origin, which distributed on areas western and eastern to Mount Taihangshan respectively. Intermediate types are also existed in some areas, which mainly distribute near the edges of depositional basins; they are usually of transitions between diluvial and lacustrine deposits. As to Neogene hard clays from Eastern China, the clay particle content is high, and montmorillonite or illite/montmorillonite turbostratic mineral is the dominating clay mineral. The content of effective montmorillonite is very high in each area, which is the basis for the undesirable engineering properties of Neogene hard clays. For hard clays from the same area, the content of effective montmorillonite in gray-greenish hard clay is much higher than that in purple-brownish or brown-yellowish hard clay, which is the reason why the gray-greenish hard clay usually has outstanding expansive property. On the other hand, purple-brownish or brown-yellowish hard clay has relatively less montmorillonite, so its property is better. All of these prove that the composition (clay mineral) of Neogene hard clay is the control factor for the engineering properties. Neogene hard clays have obvious properties such as fissured, overconsolidated and expansive, which are the main reasons that many engineering problems and geological harzards usually occur in Neogene hard clays. The paper systematically elaborates the engineering properties of Neogene hard clays from Eastern China, analyses the relationships between engineering properties and basic indexes. The author introduces the ANN method into the prediction of engineering property indexes of hard clays, which provides a new way for quantitatively assessment and prediction of engineering property indexes. During investigation in the field, the author found that there exists obvious seam-sheared zone between different hard clays in Miocene Xiacaowan formation in Xu-Huai area. Similar phenomenon also exists near the borderline between Neogene hard clays and underlying coal measures in the Southwest of Shandong province, which could be observed in the cores. The discovery of seam-sheard zone has important theoretical and practical significance for engineering stability analysis and revealing the origin of fissures in Neogene hard clays. The macrostructure, medium structure and microstructure together control the engineering properties of hard clays. The author analyses and summarizes the structural effects on hard clays in detail. The complex of the strength property of hard clays is mostly related to the characteristics of fissures, which is one of the main factors that affect the choice of shear strength parameters. So structure-control theory must be inseparably combined with composition-control theory during the engineering geological and rock/soil mechanics research of hard clays. The engineering properties, such as fissured, overconsolidated and expansive, control the instability of engineering behaviors of Neogene hard clays under the condition of excavation, i.e. very sensitive to the change of existence environment. Based on test data analysis, the author elaborates the effects of engineering environment change on the engineering properties. Taking Nanyang basin as example, the author utilizes FEM to study the effects of various factors on stability of cutting canal slopes, than sets forth the characteristics, development laws and formation mechanism of the deformation and failure of hard clay canal slopes, summarizes the protection and reinforcement principles, as well as the protection and remedy steps. On the basis of comparison of engineering properties of domestic and foreign Neogene muddy deposits, in the view of whole globe and associated with the geological characteristics of China, the paper demonstrates that the intermediate type of the material between the soil and the rock, named "hard clay/soft rock", which can not be separated abruptly, really exists in China. The author has given a preliminary classification based on its geological origin and distribution law, which is very significant for promoting the mixture of Engineering Geology, Soil Mechanics and Rock Mechanics. In the course of large scales engineering construction in China, many engineering experiences and testing data are gained, summarizing these testing results and automatically managing them with computer technology are very necessary. The author develops a software named "Hard Clay-Soft Rock Engineering Geological Information Management and Analysis System (HRGIMS)", realizes the automatic and visual management of geo-engineering information, on the basis of information management, the functions of test data analysis and engineering property prediction are strengthened. This system has well merits for practice and popularization.

黄土高原粉尘堆积源区环境及风化历史初步研究

In this study, we examined the surface features of quartz grains, the quartz oxygen isotopic ratios and the mineralogical compositions of the loess - paleosol - red clay sediments systematically. The surface features of quartz grains do not show significant changes of the dust deposits through the past seven million years. The particles were mainly created in the process of glacial and frost weathering of high mountains. Then the surfaces were altered in some degree by the flood and wind abrasion. The surface features registered all these processes. The assemblages of surface features changed for four times in the past seven million years, the occurrence ages are: 5.0~4.2MaBP, about 3.6MaBP, about 2.6MaBP and about 0.9MaBP, respectively. This may indicate that there were uplift events of the Tibetan Plateau during those times. The oxygen isotopic compositions of quartz in the sediments represent the oxygen isotopic compositions of the initial dusts because of the stable properties of quartz both physically and chemically. The oxygen isotopic compositions of 4~16um quartz changed significantly at about 2.6MaBP, decreasing from about 19.5%o to about 18.5%o. This decrease of quartz oxygen isotopic ratio suggests that the environments of the dust source areas changed at that time, or the range of dust source area changed at that time. The environmental change may result from the structural evolution of the Tibetan Plateau and global cooling at that time. The coarse fractions (>30μm) of the dust deposits were examined using the EDXA device for mineral identification. The quartz content has a decrease trend during 7~2MaBP, then increase rapidly at about 2MaBP. After 2MaBP, quartz content continues to decrease. The Ca-plagioclase content / quartz content ratio increase at about 3.6MaBP. The ratio shows a peak of 3-6 fold values at about 2.5~1.8MaBP, the cause of this is still unknown. The Ca-plagioclase content / quartz content ratio continues to increase after 1 MaBP. The flowing can be regarded as the conclusion remarks of this study: Some of the red clay sediment of the Chinese Loess Plateau (at least Lingtai and Jingchuan red clays) is eolian in origin. The quartz grains from dust deposits throughout the past seven million yeas showed the clues of glacial and frost processes. This indicates that the high mountains of western China reached a certain altitude to favor the glacial and/or frost processes at least seven millions years before. The weathering intensities of the past seven nnillion yeas have a decreasing trend. In about 5~4.5MaBP, the weathering is relatively weak, and the dust supply is relatively low. At about 3.6MaBP and 2.6MaBP, the dust supply increased significantly. The mineralogical composition, the quartz surface feature and the quartz oxygen isotope composition were influenced by the uplift of the Tibetan Plateau. The Plateau may have reached a certain altitude to generate the arid regions of inland China and favor the glacial and frost weathering. And it underwent a phased uplift, which have uplift events at about 3.6MaBP and 2.6MaBP.